CN101314640A - A kind of preparation method of water dilutable quaternary ammonium salt modified polysiloxane microemulsion - Google Patents

Abstract

The present invention relates to a kind of preparation method of water dilutable quaternary ammonium salt modified polysiloxane microemulsion, it is by adopting pre-emulsion method, siloxane oligomer and quaternized ammonium siloxane or its hydrolyzate , or prepared by microemulsion copolymerization with a composition capable of generating quaternary ammonium siloxane (or hydrolyzate). The preparation method of the quaternary ammonium salt modified polysiloxane microemulsion is simple, the molecular weight of the quaternary ammonium salt modified polysiloxane can also be adjusted, and the microemulsion does not become turbid when diluted with water. This microemulsion product is suitable for use as a personal care product and a fabric finish.

Description

A kind of preparation method of water dilutable quaternary ammonium salt modified polysiloxane microemulsion

technical field

The invention relates to a preparation method of a quaternary ammonium salt modified polysiloxane microemulsion, in particular to a preparation method of a water dilutable quaternary ammonium salt modified polysiloxane microemulsion. This microemulsion is mainly used in personal care products and fabric finishing agents, and belongs to the field of fine chemicals.

Background technique

Due to its unique structure, polysiloxane has the characteristics of soft texture, low surface energy, physiological inertia, high and low temperature resistance, waterproof and breathable, etc. Polysiloxane emulsions have been used as high-grade fabric finishing agents, cosmetics and waterproof coatings, and are favored by people. Microemulsion is a thermodynamically stable system with smaller particle size than ordinary emulsion, and its permeability and stability are better than ordinary emulsion. Quaternary ammonium salt modified polysiloxane, that is, polysiloxane molecules contain quaternary ammonium functional groups -N ⁺ R ¹ R ² R ³ X ^- , wherein R ¹ and R ² are alkyl groups with 1 to 20 carbon atoms , preferably methyl; R ³ is an alkyl group, alkaryl group, aralkyl group, or hydroxyalkyl group with 1 to 20 carbon atoms; in addition, two of R ⁵ , R ⁶ and R ⁷ can also be combined with N The atoms are connected to form a heterocyclic tertiary amine; X is a halogen such as chlorine, bromine, iodine or a methanesulfonic acid group. In addition to the common properties of ordinary polysiloxane microemulsions (transparent or translucent, good storage stability, excellent permeability, film-forming properties, etc.), its microemulsion also has bactericidal and antibacterial effects, making it widely used in personal care. There is a huge market for textiles and fabric finishes.

The preparation method of the modified polysiloxane microemulsion is mostly prepared by a two-step method at present, that is, the modified polysiloxane is first synthesized by bulk polymerization, and then microemulsified. This method is complex and takes a long time. Since microemulsions often need to add additional additives, the microemulsion prepared in this way tends to become cloudy when diluted with water. Moreover, this method is only suitable for microemulsification of modified polysiloxanes with low and medium degrees of polymerization, but it is difficult to microemulsify modified polysiloxanes with high degrees of polymerization.

Chinese patent CN1670057A (2005.9.21), titled "Preparation method of modified silicone microemulsion for fabric softener", discloses the use of pre-emulsion method, D4, water, aminosilane coupling agent, prepared by microemulsion copolymerization Amino-modified polysiloxane microemulsion. The method is simple and can prepare amino-modified polysiloxane microemulsions with a high degree of polymerization, but the catalyst used in this patent is limited to acidic catalysts, dodecylbenzenesulfonic acid (DBSA), and does not involve basic catalysts; In addition, this patent does not relate to the preparation method of how to prepare the quaternary ammonium salt modified polysiloxane microemulsion.

There are not many reports on the preparation of quaternary ammonium salt-modified polysiloxane microemulsions. US Patent US6787603B (2004.9.7), titled "Method of making emulsion containing quaternary ammonium functional silanes and siloxanes", discloses a method for preparing emulsion or microemulsion of quaternized ammonium silane or siloxane by mechanical stirring. But the quaternary ammonium salt-modified polysiloxane microemulsion prepared by this method should use amino-modified polysiloxane as raw material, and its degree of polymerization cannot be too high, otherwise, it is impossible to prepare quaternary ammonium salt-modified polysiloxane Microemulsion; In addition, this quaternary ammonium salt modified polysiloxane is the so-called kenna siloxane, that is, the molecule is limited to -CH(R ⁴ )CH(OH)YN ⁺ (R ⁵ )(R ⁶ ) (R ⁷ ) X ^- quaternary ammonium functional group (R ⁴ is alkyl or hydrogen, R ⁵ to R ⁷ are independently alkyl, preferably methyl, dodecyl or octadecyl; Y is alkylene X ^- is a counter ion.); Moreover, this method can only prepare W/O type quaternary ammonium salt modified polysiloxane microemulsion, and cannot prepare O/W type quaternary ammonium salt modified polysiloxane microemulsion .

Contents of the invention

The invention overcomes the shortcomings of the above inventions and relates to a preparation method of dilutable quaternary ammonium salt modified polysiloxane microemulsion. It consists of the following steps:

1) Siloxane oligomer, water, surfactant, optional quaternized alkoxysilane or its hydrolyzate or a composition capable of reacting to form quaternized alkoxysilane or its hydrolyzate, non-essential Necessary other types of alkoxysilane or its hydrolyzate, optional other additives high shear emulsification into a pre-emulsion.

2) Slowly drop the above-mentioned pre-emulsion into the reactor containing surfactant, water and polymerization catalyst, and keep stirring. The reaction temperature is controlled at 60° C. to 95° C., and the dropping time is 0.5 hours to 3 hours. If the pre-emulsion in step 1) does not contain quaternized alkoxysilane or its hydrolyzate or a composition that can react to generate quaternized alkoxysilane and its hydrolyzate, other types of non-essential alkoxysilane or Its hydrolyzate, and optional other additives, then add their mixed solution with water dropwise to the reaction solution, and the dropping time is 0.5 hour to 3 hours. Or mix them with the pre-emulsion and drop them into the reaction solution to participate in the polymerization reaction.

3) The above reaction solution is placed at a suitable temperature for 0 hours to 72 hours, neutralized, filtered, and discharged to obtain a transparent or translucent quaternary ammonium salt-modified polysiloxane microemulsion primary product.

4) Add optional other additives to the primary product of the quaternary ammonium salt modified polysiloxane microemulsion and stir evenly, or dilute with water if necessary, to obtain the final product of the quaternary ammonium salt modified polysiloxane microemulsion

The heating method in this preparation method is not limited to a conventional heating method, and may also be other heating methods such as microwave heating.

The siloxane oligomer referred to in step 1) can be cyclic, and its general structure is (R ⁸ R ⁹ SiO) _n (R ⁸ and R ⁹ are hydrogen, monovalent alkyl, vinyl, phenyl, etc. ; n is 3 to 6), such as hexamethylcyclotrisiloxane (D ₃ ) or octamethylcyclotetrasiloxane (D ₄ ) or decamethylcyclopentasiloxane (D ₅ ) or twelve Methylcyclohexasiloxane (D ₆ ) or their mixture (DMC); it can also be linear, and the general structure is HO(R ⁸ R ⁹ SiO) _n H (R ⁸ and R ⁹ are hydrogen, monovalent Alkyl, vinyl, phenyl, etc.; n is 3 to 300), such as hydroxy silicone oil with a low degree of polymerization; it can also be a mixture of cyclic siloxane oligomers and linear siloxane oligomers.

The quaternized alkoxysilane or its hydrolyzate referred to in step 1) or step 2) refers to a compound containing quaternary ammonium functionality in the alkoxysilane molecule or its hydrolyzate. The specific synthesis method can refer to Peng Zhongli and others published the paper "Synthesis of Quaternary Ammonium Methyldiethoxysilane" in "Fine Chemical Industry" (2006, 23(9): 873-877); it can react to generate quaternized alkoxysilane and hydrolyze The composition of the substance refers to the substance that is easy to react to generate quaternized alkoxysilane and hydrolyzate in the presence of water and surfactant, such as Chinese patent, application number 02821147.2, application date 2002.9.30, equivalent to the description in US patent US6607717 Composition of aminosilicone and epoxy compound with quaternary ammonium functionality. There are no restrictions on the type and number of alkoxy functional groups of the quaternized alkoxysilane and other types of alkoxysilanes, and difunctional and trifunctional methoxy or ethoxysilanes are preferred.

Non-essential other types of alkoxysilanes or their hydrolyzates referred to in step 1) or step 2) can improve or improve the quaternary ammonium-modified polysiloxane microemulsion with the function of removing quaternary ammonium Other functional siloxanes, such as siloxanes with amino groups, epoxy groups, vinyl groups, carboxyl groups, etc., or their hydrolysates.

The surfactant indicated in step 1) and step 2) can be nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, or their mixture, preferably nonionic surfactant. The selected non-ionic surfactant can be fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, behenyl alcohol fatty acid ester, behenyl alcohol polyoxyethylene ether, alkyl glycoside, etc. Types of nonionic surfactants, or their composition, preferably fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or their composition. Anionic surfactant can be selected derivatives of sulfonic acid and its salt, fatty acid salt, alkali metal sulfate etc., the present invention is preferably dodecylbenzenesulfonic acid; Cationic surfactant is that contains quaternary ammonium hydrophilic Part of the compound, the present invention is preferably two long-chain alkyl dimethyl ammonium halides and long-chain alkyl trimethyl ammonium halides, such as hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide Ammonium etc. If use acidic catalyst in step 2, then surfactant is preferably nonionic surfactant or anionic surfactant, composition between them. If a basic catalyst is used in step 2), the surfactant is preferably a nonionic surfactant or a cationic surfactant, or a combination thereof.

The polymerization catalyst described in step 2) can be that sulfuric acid, hydrochloric acid, strongly acidic exchange resin or other acidic substances are acidic catalysts, and the present invention is preferably dodecylbenzenesulfonic acid; it can also be alkali metal hydroxide, alkali Basic catalysts such as metal alkoxides or quaternary ammonium bases are preferably quaternary ammonium bases generated by the action of alkali metal hydroxides and quaternary ammonium salts in the present invention.

Optional additives in the preparation method include one of the following substances or their combination: (A) conditioner, such as cationic polymer, cationic surfactant, natural oil, protein, quaternary ammonium salt modified polysiloxane (B) co-surfactants, such as betaine, fatty alcohol amides, etc.; (C) humectants, such as polyols, etc.; (D) preservatives, such as formaldehyde, salicylic acid, sodium benzoate etc.; (E) freeze/thaw stabilizers, such as glycerin, ethylene glycol, etc.; (F) corrosion inhibitors, such as chromate, polyphosphate, octadecylamine, etc.; (H) other additives.

The amount of each component in the pre-emulsion in step 1) is: siloxane oligomer 20-60% by weight, surfactant 2-30% by weight, optional quaternized alkoxysilane or its hydrolyzate Or 0.025-3% by weight of the composition capable of reacting to form quaternized alkoxysilane and its hydrolyzate, 0.025-3% by weight of optional other types of alkoxysilane or its hydrolyzate, and 38-78% by weight of water.

In the total reaction mixture, the amount of siloxane oligomer is 5 to 30% by weight, the surfactant accounts for 5 to 60% by weight of the siloxane oligomer, and the quaternized alkoxysilane or its hydrolysis Compounds or compositions capable of reacting to form quaternized alkoxysilanes and hydrolyzates account for 0.1 to 10% by weight of siloxane oligomers, and 0.1 to 10% by weight of other types of alkoxysilanes or their hydrolysates, The amount of the polymerization catalyst accounts for 5 to 50% by weight of the siloxane oligomer.

The equipment used to prepare the pre-emulsion in step 1) is not limited, high-speed mixer, high-shear emulsifier, high-pressure homogenizer or other equipment can be used.

In step 2), the reaction temperature is controlled at 60°C to 95°C, preferably 75°C to 85°C in the present invention, and the pre-emulsion adding time is 0.5 to 3 hours, preferably 1 to 2 hours in the present invention. If the pre-emulsion in step 1) does not contain optional quaternized alkoxysilane or its hydrolyzate or a composition capable of reacting to form quaternized alkoxysilane and its hydrolyzate, and optional other types of alkanes Oxysilane or its hydrolyzate, then in step 2, drop the mixed solution of these substances, water, and optional surfactant to the reactor, and the dropping time is 0.5 hour to 3 hours, and the present invention is preferably 1 hour to 2 hours.

In step 3), it can be obtained by placing the reaction solution at different temperatures and equilibrating for a period of time according to the molecular weight of the quaternary ammonium salt-modified polysiloxane required. Generally speaking, the higher the equilibrium temperature, the smaller the molecular weight of the quaternary ammonium salt modified polysiloxane. The equilibrium temperature is between 0°C to 100°C, preferably 5°C to 60°C. The equilibration time is 1 hour to 72 hours, preferably 12 hours to 48 hours. Quaternary ammonium salt modified polysiloxane molecular weight size determination can measure their viscosity-average molecular weight expression with Ubbelohde viscometer, concrete operation is with reference to Sun Erkang, Xu Weiqing, " physical chemistry experiment " book (Nanjing University press publication, 1998: 188～190); the calculation of viscosity-average molecular weight refers to the paper "Microscopicity of Octamethylcyclotetrasiloxane" published by Xu Shen, Dai Jianhua, Zhao Ning and others in "Applied Chemistry", Volume 22, No. Emulsion Polymerization".

If acid catalyst is used during polymerization, then after the reaction finishes, use alkaline neutralizer, as triethanolamine, sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution etc., the present invention is preferably triethanolamine and Sodium bicarbonate in water. If basic catalyst is used during polymerization, then after the reaction finishes, use acidic neutralizer, such as dilute hydrochloric acid, dilute sulfuric acid, phosphoric acid, acetic acid etc., the present invention is preferably dilute hydrochloric acid and acetic acid.

The solid content of the quaternary ammonium salt modified polysiloxane microemulsion of the present invention is 5～30%, and appearance is transparent or translucent, and the light transmittance that records at 721 spectrophotometer (testing wavelength is 720nm) is greater than 70%, When the microemulsion is diluted several times with water, the light transmittance of the microemulsion has no obvious change. The microemulsion can be used in personal care products and fabric finishing.

Detailed ways

The examples are illustrative rather than restrictive.

Example 1

Mix 125.0 grams of octamethylcyclotetrasiloxane (D ₄ ), 23.0 grams of complex fatty alcohol polyoxyethylene ether emulsifier, and 100.2 grams of water in a beaker, and then emulsify at high speed in a high-shear emulsifier to form a pre-emulsion , _D4 accounts for 50.4% of the total amount in the pre-emulsion, and the compound emulsifier accounts for 18.4% of the _D4 mass.

Get 21 grams of the above-mentioned pre-emulsion and pour it into a constant pressure funnel, then slowly drop it into a container filled with 3.158 grams of dodecylbenzenesulfonic acid (DBSA), 0.67 grams of compound fatty alcohol polyoxyethylene ether emulsifier, and 30.6 grams of water. In a three-necked flask equipped with a condenser, stir the reaction solution and control the reaction temperature at about 75°C, and the pre-emulsion will be dripped in about 2 hours. Close the constant pressure funnel plunger, and pack with 0.108 gram of diethoxymethylsilylpropyl dimethyl octadecyl ammonium chloride (purity is 86.6%), 0.3 gram of compound fatty alcohol polyoxyethylene ether emulsifier, A mixed solution of 2 grams of water; open the constant pressure funnel piston, and drop the above mixed solution into a three-necked flask within 1 hour. During the dropping process, keep stirring the reaction solution and control the reaction temperature at about 75°C; , keep warm for 15 minutes, cool, neutralize with triethanolamine to a pH value of about 7, and obtain the quaternary ammonium salt modified polysiloxane microemulsion product, in which the quaternary ammonium salt modified polysiloxane accounts for the total amount of the microemulsion. The quaternary ammonium modified polysiloxane unit accounts for 1% of the total structural units of the quaternary ammonium modified polysiloxane, and the light transmittance is 82%. The product is diluted 2 times and 4 times with water, and its light transmittance is 85% and 83% respectively.

Example 2

Prepare pre-emulsion and quaternary ammonium salt modified polysiloxane microemulsion according to the method described in Example 1, the difference is that the mixed solution of quaternized alkoxysilane and emulsifier is directly added to the pre-emulsion and mixed uniformly Finally, it is added dropwise to the three-necked flask together with the pre-emulsion to participate in the polymerization reaction; and, in the final quaternary ammonium modified polysiloxane microemulsion product, the quaternized ammonium siloxane unit accounts for the total amount of the quaternary ammonium salt modified polysiloxane. 1.5% of structural units. The light transmittance of the product is 72%.

Example 3

The pre-emulsion was prepared according to the method described in Example 1, the difference being that in the pre-emulsion, _D4 accounted for 50.0% of the total amount, and the composite emulsifier accounted for 20.0% of the _D4 mass.

63 grams of the above-mentioned pre-emulsion is poured into a constant pressure funnel, and then slowly dripped into a container containing 9.463 grams of dodecylbenzenesulfonic acid (DBSA), 2.27 grams of compound fatty alcohol polyoxyethylene ether emulsifier, and 91.82 grams of water. In a three-necked flask with a condenser tube, stir the reaction solution and control the reaction temperature at about 75°C, and the pre-emulsion will be dripped in about 2 hours. Close the constant pressure funnel plunger, and pack with 0.473 gram of diethoxymethylsilylpropyl dimethyl octadecyl ammonium chloride (purity is 86.6%), 1.802 grams of compound fatty alcohol polyoxyethylene ether emulsifier, A mixed solution of 12 grams of water; open the constant pressure funnel piston, and drop the above mixed solution into a three-necked flask within 1 hour. During the dropping process, keep stirring the reaction solution and control the reaction temperature at about 75°C; , keep warm for 15 minutes, take out a part to cool, neutralize with triethanolamine to a pH value of about 7, test its light transmittance, and its light transmittance is 89.1%. Divide the unneutralized quaternary ammonium salt-modified polysiloxane microemulsion product into three parts, put them into glass bottles and seal them, and place them in the environment of 10 °C, 23 °C and 60 °C for 24 hours, and then use triethanolamine Neutralize and break the emulsion with isoamyl alcohol, separate the silicone oil and wash it with water three times, then place it in an oven at 130°C for 2 hours; take it out, cool it down, and then distill the product under reduced pressure to remove residual water and isoamyl alcohol. Then the measurement of the viscosity average molecular weight was carried out. Among them, the product placed at 60°C is divided into two parts after vacuum distillation, one part is used for the measurement of viscosity average molecular weight; the other part is washed three times with concentrated sulfuric acid, and after three times with water, add 50% methanol solution and stir evenly. Add a drop of phenolphthalein solution, neutralize it with ammonia water, separate the silicone oil, and carry out vacuum distillation to remove low boilers, then use it for nuclear magnetic resonance spectroscopy test. CH ₃ -( CH ₂ ) ₁₅ -CH ₂ -CH _{2 -N} ⁺ - -CH ₂ appears at δ=1.294ppm in the hydrogen nuclear magnetic resonance spectrum ( ¹ H NMR) of quaternary ammonium salt modified polysiloxane -CH 3 -(CH 2 ) 15 -CH 2 -CH 2 -N + -CH ₂ -characteristic peaks appear in the figure of -CH ₃ -( CH ₂ ) ₁₅ -CH ₂ -CH ₂ -N ⁺ - in its carbon nuclear magnetic resonance spectrum ( ¹³ C NMR) figure, explain Copolymerization of D ₄ and quaternized alkoxysilane occurred. The equilibrium viscosity-average molecular weights of quaternary ammonium salt-modified polysiloxanes at various temperatures are shown in Table 1.

The equilibrium viscosity-average molecular weight (M _{viscosity-average} ) of quaternary ammonium salt modified polysiloxane under table 1 different temperatures

Example 4

100.1 grams of octamethylcyclotetrasiloxane (D ₄ ), 22.0 grams of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether composite emulsifier, and 166.2 grams of water were stirred and mixed in a beaker, and then mixed under high shear In the emulsifier, it is emulsified at high speed to form a pre-emulsion. In the pre-emulsion, _D4 accounts for 34.7% of the total amount, and the composite emulsifier accounts for 22.0% of the _D4 mass.

Take 25.0 grams of the above-mentioned pre-emulsion and pour it into a constant pressure funnel, and then slowly drop it into a container containing 1.739 grams of cetyltrimethylammonium bromide (CTAB), 0.954 grams of fatty alcohol polyoxyethylene ether emulsifier, hydroxide In a three-necked flask equipped with a condenser tube of 0.191 g of sodium and 40.37 g of water, the reaction solution was stirred and the reaction temperature was controlled at about 86° C., and the pre-emulsion was dripped in about 3 hours. Close the constant pressure funnel plunger, and fill with 0.125 gram diethoxymethylsilylpropyl dimethyl octadecyl ammonium chloride (purity is 86.6%), the mixed solution of 4.2 grams of water; Open the constant pressure funnel plunger , drop the above mixed solution into a three-necked flask within 15 minutes. During the dropping process, keep stirring the reaction solution and control the reaction temperature at about 86°C; after the mixed solution is dropped, cool and neutralize with dilute hydrochloric acid until the pH 7 or so, filter to obtain the quaternary ammonium salt modified polysiloxane microemulsion product, in which the quaternary ammonium modified polysiloxane accounts for 11.8% of the total amount of the microemulsion, and the quaternary ammonium siloxane unit accounts for quaternary ammonium 1.44% of the total structural units of the salt-modified polysiloxane, 33% of the composite nonionic emulsifier relative to the quality of _D4 , 20% of CTAB relative to the quality of _D4 , and the light transmittance of the microemulsion is 90%.

Example 5

The pre-emulsion was prepared according to the method described in Example 1, the difference being that in the pre-emulsion, _D4 accounted for 50.0% of the total amount, and the composite emulsifier accounted for 22.8% of the _D4 mass.

Take 17.356 grams of the above-mentioned pre-emulsion and pour it into a constant pressure funnel, then slowly drop it into a container containing 1.739 grams of cetyltrimethylammonium bromide (CTAB) and 0.963 grams of compound fatty alcohol polyoxyethylene ether compound emulsifier. , 0.193 grams of sodium hydroxide, and 17.44 grams of water in a three-necked flask equipped with a condenser, the reaction solution was stirred and the reaction temperature was controlled at about 80° C., and the pre-emulsion was dripped in about 1 hour and 15 minutes. Close the constant pressure funnel plunger, and fill with 0.137 gram diethoxymethylsilylpropyl dimethyl octadecyl ammonium chloride (purity is 86.6%), the mixed solution of 1.603 grams of water; Open the constant pressure funnel plunger , drop the above mixed solution into a three-necked flask within 15 minutes. During the dropping process, keep stirring the reaction solution and control the reaction temperature at about 80°C; after the mixed solution is dropped, cool and neutralize with dilute hydrochloric acid until the pH 7 or so, filter to obtain the quaternary ammonium salt modified polysiloxane microemulsion product, in which the quaternary ammonium salt modified polysiloxane accounts for 22% of the microemulsion total amount, and the quaternary ammonium siloxane unit accounts for quaternary ammonium 1.34% of the total structural unit of the ammonium salt modified polysiloxane, 33% of the composite nonionic emulsifier relative to the quality of _D4 , 20% of CTAB relative to the quality of _D4 , and the light transmittance of the microemulsion is 84%.

Example 6

Get the pre-emulsion 69.438 grams that embodiment 5 prepares and pour in a constant pressure funnel, then slowly drip into and fill cetyltrimethylammonium bromide (CTAB) 6.959 grams, compound fatty alcohol polyoxyethylene ether emulsifier 2.83 grams, 0.767 grams of sodium hydroxide, and 87.41 grams of water in a three-necked flask equipped with a condenser, stirred the reaction solution and controlled the reaction temperature at about 80°C, and the pre-emulsion was dripped in about 1 hour and 15 minutes. Close the constant pressure funnel plunger, and fill with 0.691 gram of diethoxymethylsilylpropyl dimethyl octadecyl ammonium chloride (purity is 86.6%), the mixed solution of 4.462 grams of water; Open the constant pressure funnel plunger , drop the above mixed solution into a three-necked flask within 15 minutes. During the dropping process, keep stirring the reaction solution and control the reaction temperature at about 80°C; The value is about 7, and filtered to obtain the quaternary ammonium salt modified polysiloxane microemulsion product. In this product, the quaternary ammonium salt modified polysiloxane accounts for 20.1% of the total amount of the microemulsion, and the quaternized ammonium siloxane unit Accounting for 1.95% of the total structural units of the quaternary ammonium salt modified polysiloxane, the composite nonionic emulsifier is 31% relative to the mass of _D4 , CTAB is 20% relative to the mass of _D4 , and its light transmittance is 88%. The product is diluted 2 times and 4 times with water, and its light transmittance is 84% and 85% respectively.

Divide the unneutralized quaternary ammonium salt-modified polysiloxane microemulsion product into three parts, put them into glass bottles and seal them, place them in the environment of 19°C and 40°C for 25 hours, neutralize with dilute hydrochloric acid and use The isoamyl alcohol is demulsified, the silicone oil is separated and washed three times with water, and then placed in an oven at 130°C for 2 hours; after taking it out and cooling it, the product is distilled under reduced pressure to remove residual water and isoamyl alcohol. Then the measurement of the viscosity average molecular weight was carried out. Among them, the product placed at 40°C is divided into two parts after vacuum distillation, one part is used for the measurement of viscosity average molecular weight; the other part is washed three times with concentrated sulfuric acid, and after three times with water, add 50% methanol solution and stir evenly. Add a drop of phenolphthalein solution, neutralize it with ammonia water, separate the silicone oil, carry out vacuum distillation to remove the low boilers, and use it for nuclear magnetic resonance spectroscopy test. CH ₃ -( CH ₂ ) ₁₅ -CH ₂ -CH _{2 -N} ⁺ - -CH ₂ appears at δ=1.283ppm in the hydrogen nuclear magnetic resonance spectrum ( ¹ H NMR) of quaternary ammonium salt modified polysiloxane -CH ₃ -( CH ₂ ) ₁₅ -CH ₂ -CH 2 _-N ⁺ -CH ₂ -characteristic peaks appear in the figure of δ=29.48ppm in its carbon nuclear magnetic resonance spectrum ( ¹³ C NMR ), indicating that Copolymerization of D ₄ and quaternized alkoxysilane occurred. The equilibrium viscosity-average molecular weights of quaternary ammonium salt-modified polysiloxanes at various temperatures are shown in Table 2.

The equilibrium viscosity-average molecular weight (M _{viscosity-average} ) of quaternary ammonium salt modified polysiloxane under table 2 different temperatures

Claims (10)

1. a kind of preparation method of water dilutable quaternary ammonium salt modified polysiloxane microemulsion comprises the following steps: 1) Siloxane oligomer, water, surfactant, optional quaternized alkoxysilane or its hydrolyzate or a composition capable of reacting to form quaternized alkoxysilane or its hydrolyzate, non-essential Necessary other types of alkoxysilane or its hydrolyzate, optional other additives high shear emulsification into a pre-emulsion. 2) Slowly drop the above-mentioned pre-emulsion into the reactor containing surfactant, water and polymerization catalyst, and keep stirring. The reaction temperature is controlled at 60° C. to 95° C., and the dropping time is 0.5 hours to 3 hours. If the pre-emulsion in step 1) does not contain quaternized alkoxysilane or its hydrolyzate or a composition that can react to generate quaternized alkoxysilane and its hydrolyzate, other types of non-essential alkoxysilane or Its hydrolyzate, and optional other additives, then add their mixed solution with water dropwise to the reaction solution, and the dropping time is 0.5 hour to 3 hours. Or mix them with the pre-emulsion and drop them into the reaction solution to participate in the polymerization reaction. 3) The above reaction solution is placed at a suitable temperature for 0 hours to 72 hours, neutralized, filtered, and discharged to obtain a transparent or translucent quaternary ammonium salt-modified polysiloxane microemulsion primary product. 4) Add optional other additives to the primary product of the quaternary ammonium salt-modified polysiloxane microemulsion and stir evenly, or dilute with water if not necessary, to obtain the final product of the quaternary ammonium salt-modified polysiloxane microemulsion. 2. the preparation method of the quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that the quaternary ammonium salt modified polysiloxane has a linear or crosslinked structure, and the optional band in the molecule There are other functional groups such as amino group and epoxy group, which must have a quaternary ammonium functional group -N ⁺ R ¹ R ² R ³ X ^- , wherein R ¹ and R ² are alkyl groups with 1 to 20 carbon atoms, preferably methyl R ³ is an alkyl group, alkaryl group, aralkyl group, or hydroxyalkyl group of 1 to 20 carbon atoms; in addition, two of R ¹ , R ² and R ³ can also be connected with an N atom to form a hetero Cyclic tertiary amine; X is halogen such as chlorine, bromine, iodine or methanesulfonic acid group. 3. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that heating mode can be conventional heating, also can be other heating modes such as microwave heating. 4. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that the equipment used for preparing pre-emulsion can use high-speed mixer, high-shear emulsifier, high-pressure homogenizer or Other equipment capable of dispersing silicone oligomers in water. 5. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that step 1) siloxane oligomer, can be cyclic, and general structural formula is (R ⁴ R ⁵ SiO) _n (R ⁴ and R ⁵ are hydrogen, alkyl, vinyl, phenyl, etc.; n is 3 to 6), such as hexamethylcyclotrisiloxane (D ₃ ) or octamethylcyclotetra Siloxane (D ₄ ) or decamethylcyclopentasiloxane (D ₅ ) or dodecamethylcyclohexasiloxane (D ₆ ) or mixtures thereof (DMC); also linear, structure The general formula is HO(R ⁴ R ⁵ SiO) _n H (R ⁴ and R ⁵ are hydrogen, alkyl, vinyl, phenyl, etc.; n is 3 to 300), such as hydroxy silicone oil with a low degree of polymerization; it can also be A blend of cyclic and linear siloxane oligomers. 6. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that the consumption of each component in the pre-emulsion in step 1) is: siloxane oligomer 20～ 60% by weight, 2-30% by weight of surfactant, 0.025-3% by weight of optional quaternized alkoxysilane or its hydrolyzate or a composition capable of reacting to form quaternized alkoxysilane and its hydrolyzate, 0.025-3% by weight of optional other types of alkoxysilane or its hydrolyzate, and 38-78% by weight of water. 7. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that in total reaction mixture, the amount of siloxane oligomer is 5～30% by weight, the surface The active agent accounts for 5 to 60% by weight of the siloxane oligomer, and the quaternized alkoxysilane or its hydrolyzate or the composition capable of reacting to form the quaternized alkoxysilane and its hydrolyzate account for a low proportion of the siloxane. The amount of the polymer is 0.1-10% by weight, the amount of other types of alkoxysilane or its hydrolyzate is 0.1-10% by weight, and the amount of the polymerization catalyst accounts for 5-50% by weight of the siloxane oligomer. 8. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that surfactant can be nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant agent, or a mixture of them. Nonionic surfactants can be fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, behenyl alcohol fatty acid esters, behenyl alcohol polyoxyethylene ethers, alkyl glycosides, etc., and other types of non-ionic surfactants. Ionic surfactants, or their composition, preferably fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or their composition. Anionic surfactants can be selected from derivatives of sulfonic acid and its salts, fatty acid salts, alkali metal sulfates, etc. In the present invention, it is preferably dodecylbenzenesulfonic acid. Cationic surfactant is a compound containing a quaternary ammonium hydrophilic part in the molecule, and the present invention is preferably two long-chain alkyl dimethyl ammonium halides and long-chain alkyl trimethyl ammonium halides, such as hexadecyl trimethyl bromide Ammonium chloride, octadecyltrimethylammonium bromide, etc. If use acidic catalyst in step 2, then surfactant is preferably nonionic surfactant or anionic surfactant, composition between them. If a basic catalyst is used in step 2), the surfactant is preferably a nonionic surfactant or a cationic surfactant, or a combination thereof. 9. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that polymerization catalyst can be that sulfuric acid, hydrochloric acid, strongly acidic exchange resin or other acidic substances are acid catalysts, the present invention preferably It is dodecylbenzenesulfonic acid; it can also be alkaline catalysts such as alkali metal hydroxides, alkali metal alkoxides or quaternary ammonium bases, and the present invention is preferably the quaternary ammonium bases generated by the action of alkali metal hydroxides and quaternary ammonium salts . 10. the preparation method of quaternary ammonium salt modified polysiloxane microemulsion according to claim 1 is characterized in that non-essential additive can comprise a kind of following material or their composition: (A) conditioner, Such as cationic polymers, cationic surfactants, natural oils, proteins, siloxanes other than quaternary ammonium salt modified polysiloxanes, etc.; (B) co-surfactants, such as betaine, fatty alcohol amides, etc.; ( C) Moisturizers, such as polyols, etc.; (D) Preservatives, such as formaldehyde, salicylic acid, sodium benzoate, etc.; (E) Freezing/thawing stabilizers, such as glycerin, ethylene glycol, etc.; (F) Corrosion inhibitors , such as chromate, polyphosphate, octadecylamine, etc.; (H) other additives.